A cooling sensation agent that endows the skin, oral cavity, nose and throat of a person with a refresh feeling (refresh sensation) and cool feeling (cooling sensation), that is cooling sensation effect, is used in various products such as toothpastes, confectioneries such as chewing gums and candies, tobacco, cataplasms, bath agents and cosmetics. Menthol, which is the representative cooling sensation agent material, has an excellent cooling sensation effect. However as menthol is highly volatile, the cooling sensation effect thereof does not last so long. Therefore, studies have been carried out to maintain a cooling sensation action for a long period of time. Examples of the compounds having been developed to maintain the cooling sensation for a prolonged period of time include menthoxypropanediol that is glycerin ether of menthol, lactic ester of menthol, ethylene glycol ether of menthol and the like.
However, under influence of recent global warming, there has been a demand for cool feeling processing of clothing such as clothes and the like to make people feel more comfortable even in hot summer. Most cooling sensation agents including menthol, however, are highly volatile and also highly water-soluble, and thus, the cool feeling processing of clothes and the like by use of the cooling sensation agents often results in loss of the action within a short period of time. For example, even if a cooling sensation agent is compounded with a detergent or a softener, the cooling sensation agent hardly remains on the clothing fiber after washing because of its water solubility and further, no cooling sensation agent remains after drying because of its high volatility.
To solve these problems, sustained-release cooling sensation agents utilizing a chemical change has been developed. For example, a method for giving a refresh feeling to gas to be breathed at smoking by releasing a cooling sensation agent, menthol due to thermal decomposition of chlorocarbonic esters or carbonic esters contained in tobacco on combustion of tobacco (U.S. Pat. No. 3,312,226), a method for releasing a fragrance component by decomposition of carbonic esters on the skin to elongate the diffusion period of the fragrance (JP 10-95752 A), a method for releasing a fragrance due to decomposition of orthoesters by perspiration on the skin (WO 94/06441 A), and the like are mentioned. In addition to them, there are known many patents that utilize release of a fragrance molecule by decomposition of a fragrance precursor based on a chemical change or an enzyme reaction (JP 45-26872 B, EP 1077251 A, WO 95/04809 A, WO 97/16523 A, JP 8-225564 A, JP 2009-520701 A, and Angew. Chem. Int. Ed, 2007, 46, 5836-5863). JP 45-26872 B, for example, discloses cosmetics in which monomenthyl or dimenthyl esters of dicarboxylic acid is contained. The esters in the cosmetics are decomposed by an ester-hydrolyzing enzyme present in a skin or an alkali included in an alkaline cosmetic that is already applied on the skin to release menthol. However, it is not known that the aforementioned dimenthyl esters of dicarboxylic acid themselves have an excellent cooling sensation effect. In addition, when a precursor of a flavor or fragrance compound is used, there are still some problems that quite a long time is required till the decomposition reaction of the precursor starts and a flavor or fragrance compound is released after adhesion of the precursor to clothes or a skin, the strength of cooling sensation is significantly weak, and so on. Thus, it is not a fundamental solution.
Other studies on the method for providing clothes with cooling action, for example, using microcapsules or the like have been conducted, and many patent applications have been filed. Examples thereof include a fiber processing method by use of microcapsules containing mint oil or l-menthol (JP 2000-96443 A), a fiber processing method by use of a microcapsulated substance which melts at a temperature not higher than the body temperature, so that the substance gives persons a cooling action reversibly by latent heat when contacting with skin (JP 2006-161226 A), or the like. However, they have also problems. That is, in the former method, processed clothes, of course, loses its action after releasing of all cooling sensation agent by destruction of the microcapsules, and it is actually impossible to re-process the clothes at home. Further, because the stage of releasing the cooling sensation agent by destruction of the microcapsules is the rate-determining step in this method, similar to a chemical reaction, it is not currently at the technological level where the cooling action can be provided to persons just after wearing of the clothes. In the latter method which relies on phase transition between solid and liquid, the cooling action cannot be provided to persons in constantly hot areas where the microcapsulated substance does not return to the solid state after melting.
An object of the present invention is to provide a cooling sensation agent composition by which the conventional problems described above are solved, i.e., to provide a cooling sensation agent composition which shows the long-lasting cooling action for an extended period of time.
Another object of the present invention is to provide a sensory stimulation agent composition which contains the cooling sensation agent composition.
Still another object of the present invention is to provide a flavor or fragrance composition, a beverage, a food product, a perfume or cosmetic product, a toiletry product, daily utensil products and groceries, and a medicine, which contain the cooling sensation agent composition or the sensory stimulation agent composition, and also a production method of the same.
Further, still another object of the present invention is to provide a method for providing a prolonged cooling action by applying one of the aforementioned products containing the cooling sensation agent composition or the sensory stimulation agent composition directly onto a skin or a scalp, administering it into an oral cavity, or applying it on fibers, a fiber product, clothes or clothing; or a cool refreshment processing method of fibers, a fiber product, clothes or clothing by compounding a cooling sensation agent composition or the sensory stimulation agent composition with those or processing those with a cooling sensation agent composition or the sensory stimulation agent composition.
Furthermore, another object of the present invention is to provide novel diesters of dicarboxylic acid.
As a result of intensive studies to solve the problems described above, inventors of the invention found that a diester compound of dicarboxylic acid where at least one of the diester includes an alcohol residue having a para-menthane skeleton, which may have a substituent, but not all of the alcohol residues are a menthol residue, has an excellent and long-lasting cooling sensation effect. In addition, the inventors also found that the diesters may easily remain in clothes when it is compounded with a detergent, a fabric softener or the like and the clothes are washed using the detergent or rinsed using the softer, and the clothes after washing or rinsing exhibit a gentle and long-lasting cooling sensation at the time of wearing or after the wearing. Further, the inventors found that a long-lasting cool refreshing action was obtained even when the diester compound is compounded for a beverage, a food product, a perfume or cosmetic product, a toiletry product, daily utensil products or groceries, tobacco, a medicine and the like. The present invention was made based on these findings.